DE2011311A1 - Copolymers making oil and water repellent and processes for producing the same - Google Patents

Description

E, I. DU PQNT DE NiJMOUBS AIiD SQMEMiY., 1Qth and Market Streets, Wilmington, Delaware 19 898, V "St" A *

Oil and water repellent Misehpolym, erisa'te and the method of dividing them

The invention relates to new ^; Fluprubstituierte y the units of the general formula P (OFg) _n OH ₂ OH ₂ Q ₂ CGH = GH ₂ and RO ₂ OGH = CH ₂ , namely "especially units γρη acrylic acid / trifluoroethyl ester, and are used for treating textile" tilstpffen suitable to give these oil and water repellent properties. \ ·

Although many known, fluorine-containing polymers »those against ** currently used for the treatment of textile fabrics, in the Are able to use the textile material en oil ^ and ^ water repellency averm ^ - there are no special ones Difficulties in the area of rejection. the with the well-known oil and water repellent m.aphjnd Substituted Polypprisaten were not ijehpben

A splPhes problem is there © Eirh, altenbleib§n te§ Abwelsunpv§r "mögens at lügelfreigeweben vpr the Pixi§ren ftöi iüg§lf ^ eifegfzea by Wärmebehandlun§ _t The

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OR-4668 <s

Fixing heat treatment at high temperature, which only then can be made when the fabric is already ready for use Garment has been processed and has received the desired columns. Said so far as oil and water repellent fluoro-substituted polymers used can only be fixed duroh heat treatment if the garment is already finished, the textile remains unprotected against the finished product during processing Soiling with oil and grease.

Another problem is the removal of the oil and water repellent coatings from the fabric by abrasion. The surfaces of the fabric fibers are subject to abrasion through friction during bending or washing, two fabrics sliding over each other, as is the case with upholstery fabrics, and numerous other causes. Many of the known oil- and water-repellent agents based on fluorine-substituted polymers show insufficient resistance to abrasion, and therefore the fabrics treated with these substances lose their oil- and water-repellent protective coating, especially at the points of the strongest abrasion. As a result, the resistance to soiling by substances based on oil and water disappears in the same places.

Only new fluorine-substituted polymers were found the_the fabrics that are traded with them..Jbe.are unexpected Give properties. These polymers give ironing fabrics oil and water repellency prior to heat treatment as well as resistance to abrasion and consequently to the loss of repellency, whereby some problems in the field of oil and water repellency, that the apparel manufacturers are facing today will be resolved.

The invention relates to polymers which make them oil and water repellant and also make them resistant to trooken soiling.

009137/2123;

These polymers Tenthailten about 75 to 98 percent by weight of units ^ derived from monomers of the general formula R-CHgCHgOgCCHsdHg, in which R _{f is} a perfluoroalkyl group with 4 to 14 carbon atoms, and about 25 to 2 percent by weight of units derived from monomers of the general formula ROgCCH = CH _{2 are} derived, in which R has the meaning F (CFg) _n CHg- (n- ■ «1 or 2), HCFgCF ₂ CH ₂ - or (CFj) ₂ CH . ■: ■■ '■■■ " ^: ... ■■, ■' ■

It is often also expedient to add monomers of the general formula OH ^ OR ¹ OOIIH-R ² QHj, CHg = CR ¹ OOgR ⁵ OH or CHg = CR ¹ CO ₂ R ⁴ or mixtures thereof, in which R is a hydrogen atom or

a methyl group, R an alkyl group with 1 to 4 carbon atoms, R 'is an alkylene group having 2 to 4 carbon atoms and R is an epozyalkyl group having 3 or 4 carbon atoms mean. The amount of units derived from these monomers can range from 0 to 5 percent by weight vary"

Dabfei supplement the proportions of the individual monomer units in the copolymer for $ 100, and the copolymer has preferably an inherent viscosity of less than 0.8, determined on a 0.5 percent solution in Trichlorotrifluoräthjan at 30 ° C.

The new, fluorine-substituted polymers contain two essential components. The first constituent are units that are _: of a. Monomers of the general formula R ^ CHgCHgOgCCH »CHg ^ are derived, where -R _{f is} a perfluoroalkyl group having 4 to 14 carbon atoms. The polymer must contain 75 to 98 percent by weight of these units.

In these monomers R ₁ CHgCHgOgGCH = CHg, the perfluoroalkyl group R _{f is} preferably a straight-chain group F (CFg) ₈ , in which 8 has a value from 4 to 14, and preferably a mixture of these groups in which s predominantly 6 , .8., And 10, since such monomers are commercially available and not

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009B3772123

V ίΟ1131ί

OR-4668

are too costly and give the best results. Branched-chain perfluoroalkyl groups such as (OPj) ₂ OP (CP ₂ ) Bi * where s' has a value of 1 b ^ s 11 can also be used *

The monomers RfCH ₂ CH ₂ O ₂ CCH = CH ₂ can be produced by esterification of the alcohols R _f CH ₂ CH ₂ 0H in one or the other known manner, for example by reaction with aoryl acid chloride in the presence of a tertiary amine, by reaction with acrylic acid in the presence of an acidic catalyst, such as sulfuric acid or toluenesulfonic acid or a tetraalkyl titanate (USA patent 3 056 818), by reacting the iodides R ^ CH ₂ CH ₂ I with an alkali salt of acrylic acid (USA patent 3 239 557) or duroh transesterification of the Alcohols R ^ CH ₂ -CH ₂ OH with an acrylic acid alkyl ester, such as the methy], .- or ethyl ester, in the presence of an acid or of tetraalkylitanate (US Pat. No. 2,822,348). The alcohols R _f CH ₂ CH ₂ OH

are known, e.g. from U.S. Patent 3,283,012.

For the purposes of the invention, only acrylic esters R ^ CH ₂ CH ₂ O ₂ -CCHsCH ₂ may be used as monomers, since the corresponding methacrylic esters R ^ CH ₂ CH ₂ O ₂ CC (CH ^) = CH ₂ do not lead to the desired results. Furthermore, in the case of the acrylic acid esters, there must be two methylene groups between R ^ and the Es.teroarbonylgruppe; because if instead of the monomers R ^ CH ₂ CH ₂ O _{2 CCHsCH 2} acrylic acid esters of the general formula R _f CH ^ O ₂ CCH = CH ₂ (US Pat. No. 2,642 * 416) or the general formula R _f (CH ₂ ) O ₂ CCH = CH ₂ (p «3 or more *) (USA patent specification 3 102 103) are used, the desired results are again not achieved. ' _|

The second essential monomer, from which the copolymer units are derived according to the invention, is an acrylic acid ester of the general formula RO ₂ CCH = CH ₂ , in which R is F (CFg) _n CH ₂ - (n m 1-2), HCF ₂ CF. ₂ CH ₂ - or (CFj) ₂ CH-. It should be noted that all of these esters are acrylic acid esters and that the corresponding methacrylic acid esters cannot be used for the purposes of the invention. \

009837/2123

OfltäiNAL

All of the acrylic acid esters are easily obtainable by transesterification of the corresponding alcohols P (CP ₂ ) _n CH ₂ OH with acrylic acid or simple acrylic acid esters. The esters P (GPg) _n CHgO ₂ -CCH = CH ₂ (η = 1 or 2) are known compounds; cf. Codding and co-workers, Journal of Polymer Science ;, 15 (1955), page 515. The esters H (CPg) ₂ CH ₂ O ₂ CCH = CH ₂ can easily be prepared by reacting the corresponding alcohols with an acrylic acid, and the monomer (.CP ^) ₂ CHO ₂ CCH = CHg is known from ^ USA patent 3,177,185. "<

It is essential to the invention that at least 2 percent by weight, but not more than 25 percent by weight of the units of the copolymer are derived from this monomer. If the copolymer is less than 2 or more than 25 percent by weight contains centi of these monomer units, it does not indicate that it is 91 the required properties. ",!

Of the above-described itionomers of the general formula R0 ₉ CJ3H = CH ₉ , the compounds CPxCH ₉ O ₅ CCH = CH _{9 and} CP-ZCP ₉ CH ₉ O ₉ CCH = SCh _{9 are} preferred, and the preferred concentrations are in the range from about 3 to 10 percent by weight RO ₂ CGH = CH ₂ . . ■. ;

Often it is expedient if 'not ^essential; that the copolymers still contain small amounts of units which are derived from certain monomers, which can have a greater durability against dry cleaning and washing as a result. Although a satisfactory durability is already achieved without such monomer units, products of even higher durability are obtained if the polymers contain such additional monomer units. These monomer units are of the general N-hydroxyalkylacrylic acid amides. Pormel CH ₉ = CR-COHH-R OH, acrylic acid hydroxyalkyl esters of the general formula CH ₉ = CR -CO ₉ R QH or acrylic acid epoxyalkyl esters of the general formula CH ₂ = CR GQgR ■ derived, where R © in hydrogen atom or a methyl group,

INSPECTED

R ² in the amides denotes a hydroxyalkyl group with 1 to 4 carbon atoms, R in the esters denotes a hydroxyalkyl group with 2 to 4 carbon atoms and R denotes an epoxyalkyl group with 3 or 4 carbon atoms. Some of these monomers that are commercially available are N-methylolacrylic acid amide, N-methylol methacrylic acid amide, 2-hydroxyethyl acrylic and methacrylic acid, glycidyl acrylic and methacrylic acid. The other hydroxyalkylamides can be easily prepared by reacting acrylic acid or methaoryl acid chloride with hydroxyalkylamines, such as ethanolamine, 2-hydroxypropylamine, 3-hydroxypropylamine, 2-hydroxybutylamine, 3-hydroxybutylamine or 4-hydroxybutylamine. Other acrylic acid or methaoryl acid hydroxyalkyl esters can be prepared by esterifying 1 mole of acrylic or methacrylic acid with 1 mole of a diol such as 1,2-propylene diol, 1,3-propylene diol, 1,2-butylene diol, 1,3-butylene diol or 1,4-butylene diol Epoxyalkyl esters are obtained using epoxybutanols.

Commercially available monomers of this type are N-MethyIo1-acry {Ls acid amide or methacrylic acid amide, acrylic acid and

2-hydroxyethyl methacrylate and glycidyl acrylate and methacrylate, which are therefore preferred. Mixtures of several of the monomers described above can also be used can be used and may even be preferred, e.g. equal parts by weight of N-methylolacrylic acid amide and 2-hydroxyethyl methacrylate. The presence of the Units derived from these monomers in the polymers according to the invention in amounts of more than 5 percent by weight leads to undesirable effects on the properties of the Polymers, and therefore the polymers should contain such monomer units only in amounts of 0 to 5 percent by weight. The copolymers preferably contain about 0.5 percent by weight of such units, but they need. only 0.1 percent by weight of such. Units included.

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The copolymers according to the invention should not contain any significant amounts of other monomer units than those described above, because otherwise the desired properties will not be achieved.

Although the copolymer according to the invention can be produced by the known solution polymerisation methods, they are preferably produced by aqueous emulsion polymerisation. In the broadest sense can ι ^1, all known water-soluble and water-insoluble, free-radical forming Polymerieationserregfer be used. The water-soluble polymerization pathogens include inorganic peroxides, such as sodium peroxide, barium peroxide, ammonium or potassium persulfate, and water-soluble azo compounds, such as azo-bis (ieobutyramidine) dihydrochloride. The water-insoluble polymerization pathogens include peroxy anhydrides, such as benzoyl peroxide, peroxy esters, such as tert-butyl peroxytrimethylacetate, tert- butyl peroxybenzoate, hydroperoxides, such as tert-butyl hydroxide, di -hydrogen alkyl peroxides, such as III-tert.butyl peroxide, and non-alcoholic azo compounds Azo-bis (isobutyronitrile) and azobis (dimethylvaleronitrile). Redox catalysts, such as a mixture of ammonium persulfate, sodium bisulfite and ferrous sulfate, can also be used.

In general, the water-soluble azo-bi8- (ieobutyramidiny dihydrochloride is preferred as the polymerization agent, since it generally leads to the formation of uniform polymers. ;

The polymerization temperature depends on the particular Polymerization pathogen and can by the person skilled in the art on the basis of contexts known to him can be selected. :

The polymerization is carried out by first emulsifying the monomers in water, then the reaction mixture on the Heated to the desired temperature and the polymerization exciter clogs. It can be twofold, if not necessary,

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INSPECTED

be to homogenize the mixture of monomers and water before heating. Since some of the above-mentioned monomers of the general formula RO ₂ CCH = CH _{2 are} relatively low-boiling compounds that often boil below the polymerization temperature, care must be taken to ensure that these monomers remain in the reaction vessel. This can easily be achieved by placing an effective reflux condenser on the reaction vessel or by polymerizing in a closed autoclave. ;

In order to obtain aqueous emulsions, you have to add emulsifiers. For this purpose, cationic or anionic emulsifiers are used against the! non-ionic emulsifiers preferred; however, mixtures of nonionic and cationic or anionic emulsifiers can be used. Suitable cationic emulsifiers are the known quaternary ammonium salts of long-chain aliphatic amines of the general formula (R NR ^) ⁺ X ~, in which R is an alkyl group with at least 12 carbon atoms. In general, R is a lower alkyl group such as the methyl group and X "is an inert anion such as the chlorine ion. A typical group of such emulsifiers are the ammonium salts sold by the Armor Company under the trademark" Arquad " n-Alkyl-trimethylammonium chlorides, in which the alkyl group has 12 to 18, preferably 16, carbon atoms. These are the preferred cationic emulsifiers. Other types of cationic emulsifiers are the acetates of n-alkyl-dimethylamines, in which the alkyl group has 12 to. These salts are suitable as far as the polymerization is concerned, but have a somewhat detrimental effect on the washability of oily dirt which the polymers in question impart to the fabrics and are therefore not preferred.

Suitable anionic emulsifiers are alkali salts of alkanesulfonic acids and alkali salts of sulfuric acid monoalkyl esters,

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both of which have 12 to 18 carbon atoms in the alkyl group. Fatty acid soaps can also be used if they are not contain unsaturated bonds.

To achieve the best properties to the inherent viscosity of the polymers! Preferably be .Less than 0.8, determined on a 0 _r 5-.pro.zentigen solution in trichlorotrifluoroethane at 30 ° G. Die'inhärente viscosity is given by the equation ■ ■

! Vi a, -J- In

defines, in which Vi the inherent viscosity, G the polymer content in grams each! 100 ml solution, V the viscosity of the solution, the viscosity of the solvent and the natural Logarithm means. :

If necessary, small amounts of chain transfer agents * such as dodecyl meroaptan, can be added to control the molecular weight and hence the inherent viscosity keep. Preferably! the inherent viscosity of the polymers 0.1 to 0.35. Chain transfer agents are usually needed to achieve viscosities in this range.

For use in making oil and water repellent and against Approaches which make dry soiling resistant are obtained from the polymerization processes described above Polymer emulsions used directly in the padding bath without the polymer being isolated. ■

The agents are preferably applied to textiles from an aqueous dispersion by brushing, dipping, spraying, padding, whale application or any combination of these methods. For example, the concentrated polymer ^{dispersion 1} as it is obtained during the polymerization can be used as a pad bath by diluting it with water to a pesticide content of 0.1 to 10 percent by weight, based on the bath.

. ■■ '■' · - ⁹ "■ -" · - · '"■ ·. ·' J 00S837 / 2123

The fabric is padded in this bath and then, ordinary between nip rollers, freed of excess liquid, so that the dry absorption (weight of the dry Polymerisats, based on the fiber) is 0.1 to 10 percent by weight of the fiber. The treated fabric is then dried by heating, e.g. in an oven to 135 to 172 ° 0. The dry substance is oil-free without further heating. and water-repellent, but the degree of repellency can be increased slightly by further heating. The fabric retains its repellency even after repeated washing and dry cleaning.

It is common practice to treat fabrics with several agents at the same time. These agents include plasticizers, anti-wrinkle agents, oil, sagging agents, anti-static agents, resin finishes, soil release agents, and the like. If the polymers according to the invention are used in the presence of such agents, it may be necessary to use them in lower concentrations than when used on their own in order to achieve the corresponding repellency. It is also common practice to add water-repellent auxiliaries to the treatment baths. In general, much larger amounts of polymer are required to achieve the maximum water repellency than to achieve the maximum oil repellency. Technically, it's cheaper to just add so..viel polymer, as is necessary to obtain the desired oil repellency, and then the much cheaper to add water repellency means to bring das.Wasserabweisungsvermögen to the desired height.

In more recent times, the non-iron treatment has been introduced into textile technology. In this treatment, a non-iron resin, such as a resin of the composition

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HIGH ₅ N -CHOH

O = G

I.
HIGH ₂ -N -OHOH

together with the polymers according to the invention on the Fabric applied. In some cases these resins are used only then fixed by heat treatment when the textile material has already been processed into the finished product. It is It is therefore important that the textile becomes repellent as soon as it dries, as it does when the polymers are applied takes place according to the invention.

Suitable substances, which with the polymers according to the invention * · can be treated are pasers, yarns, textiles and products made from threads, pasers or yarns made from natural, modified natural or synthetic polymers or mixtures thereof. Examples are cotton wool, Silk, regenerated cellulose, polyamides, fiber-forming, linear polyesters, fiber-forming polyacrylonitrile and modified Acrylonitrile polymers, cellulose nitrate, cellulose acetate, Fiberglass and the like. These can come in many different forms, e.g. as knitwear, knitwear and woven goods, such as Atlas, poplin, shirt cloth, jean gabardine, upholstery fabrics, nonwovens and the like for the production of rainwear, Work clothes, suits, women's clothes, tent fabrics, body blankets, Upholstery fabrics, fabrics for decorative purposes and for many other purposes. *.

In the following examples, all quantitative data relate to on weight.

The monomers of the general formula R ^ CH ₂ CH ₂ O ₂ GCH = CH ₂ are prepared by reacting the iodides R _f t3H ₂ CH ₂ J with ethyl acrylate.

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example 1

An aqueous dispersion is made from 16 parts of a 50 percent solution of octadecyltrimethylammonium chloride, 144 parts of R ^ CH ₂ CH ₂ O ₂ CCH = OH ₂ , where R _{f is} a mixture of perfluoroalkyl groups Rf (CF ₂ ) _n - and η is values of 6, 8, 10, 12 and 14 in a ratio of 35: 30: 18: 8: 3 and made 80 parts of water. The dispersion is diluted with 48 parts of water, whereupon nitrogen is passed in for 30 minutes, 0.095 part of 2-hydroxyethyl methacrylate and 0.145 part of 60 percent aqueous N-methylolacrylic acid amide are added and nitrogen is passed through for a further 30 minutes. Then sets to 16 parts of acrylic acid 2, 2, 2-trifluoräthylester to, diluting the dispersion with further 75 parts of water and heated under nitrogen to 65 ° C. After the addition of 0.32 parts azobis (isobutyramidine dihydrochloride) is the mixture was kept at 65 to 70 ° C. for a further 8 hours. · ^:

Analysis of the dry polymer shows that the monomer units are contained in the copolymer in approximately the same ratio in which the monomers were used, ie 90 1> R ₁ —CH ₂ CH ₂ O ₂ CCH =CH ₂ , 10 CF ₅ CH ₂ O ₂ CCH = CH ₂ and 0.25 # HOCH ₂ CH ₂ O ₂ CC (CH ₅ ) = CH ₂ and CH ₂ = CHCOKHCH ₂ Oh each. The polymer has an inherent viscosity of 0.245, determined on a 0.5 percent solution in trichlorotrifluoroethane at 30 ° C.

Example 2

The procedure is as in Example 1, but with 16 parts of 2,2,3,3,3-pentafluoropropyl acrylate instead of the 16 parts of trifluoroethyl acrylate. The polymer obtained in this way contains 90 i> H _f CH ₂ CH ₂ O ₂ CCH = CH ₂ , 10 £ CF ₅ CF ₂ CH ₂ O ₂ CCH = CH ₂ and 0.25 1> HOCH ₂ CH ₂ O ₂ CC ( CH ₅ ) = CH ₂ and CH ₂ = CHCONHCh ₂ OH and has an inherent viscosity of 0.305, determined on a 0.5 percent solution in trichlorotrifluoroethane at 30 ° 0.

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Example 3

The procedure is as in Example 1, but with 152 parts of R _f CH ₂ CH ₂ -O ₂ CCH = CH ₂ instead of 144 parts of the same monomer and 8 parts of H (CPg) ₂ CH ₂ O ₂ CCH = CH ₂ ^{ans; fcelle the} ^ parts of acrylic acid trifluoroethyl ester. The polymer obtained in this way contains 95 # R _f CH ₂ CH ₂ O ₂ CCH = CH _2,. 5 1 » H (OPg) ₂ CH ₂ GCH = CH ₂ and each 0.25 & HOCH ₂ CH ₂ O ₂ CC (OH,) = CH ₂ and aH ₂ = CHC0NHCH ₂ 0H and has an inherent viscosity of 0.360," determined on a 075 percent solution in Trichlorotrifiuoräthan at 30 ° C.

Example 4

The procedure is as in Example 1 using R ^ CH ₂₂₂ CGH = CH ₂ and 16 parts of H (CF ₂ I) ₂ CH ₂ O ₂ CCH = CH ₂ . The polymer obtained in this way contains 90 # R ^ H ₂ CH ₂ O ₂ CCH = CH ₂ , 10 <f * Η (σΡ ₂ ) ₂ σΗ ₂ -O ₂ CCH = CH ₂ and 0.25 1 * CH ₂ = C each (CH ₅ ) CO ₂ CH ₂ CH ₂ Oh and CH ₂ = CHCONH-CH ₂ OH and has an inherent viscosity of 0.340 »determined on a 0.5 percent solution in trichlorotrifluorethane

30 ° C.

B e

: i s ρ i e 1

The procedure is as in Example Λ using 128 parts of R _f CH ₂ CH ₂ O ₂ CCH = CH ₂ and 32 parts of H (CP ₂ ) ₂ CH ₂ OCH = CH ₂ . The polymer obtained in this way contains 80 ' $ R ^ CH ₂ O ₂ CCH = CH ₂ , 20 $> H (CPg) ₂ -CH ₂ O ₂ CCH = CH ₂ and 0.25 ^ CH ₂ = C (CH ₅ ) each CO ₂ Ch ₂ OH ₂ OH and CH ₂ = CHCO-NHCH ₂ OH and has an inherent viscosity of 0.33 pounds, determined on a 0.5 percent solution in trichlorotrifluorethane at 30 ° C. -

Example 6

One works according to Example 1 using. 152 parts of R _f CH ₂ CH ₂ 0 ₂ CC (CH ₅ ) = CH ₂ and 8 parts (CP ₅ J ₂ CHO ₂ CCH = CH _2. The polymer obtained in this way contains 95 % of R _f OH ₂ CH ₂ O ₂ CCH = CH ₂ , 5 $> (CP ₅ J ₂ CHO ₂ CCH = CH ₂ and each 0.25 ^ OH ₂ = C (CH ₅ ) Co ₂ CH ₂ CH ₂ OH and 'CH ₂ = CHOONHCh ₂ OH and has a inherent viscosity vpn 0.465,

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determined on a 0.5 percent solution in trichlorotrifluoroethane at 30 ° C.

Example 7

The procedure is as in Example 1 using 152 parts of R ^ CH ₂ CH ₂ O ₂ CCH = CH ₂ and 8 parts of trifluoroethyl acrylate. The polymer obtained in this way contains 95 # R _f CH ₂ CH ₂ O ₂ CCH = CH ₂ , · 5 $> CP ₃ CH ₂ O ₂ CCH = CH ₂ and 0.25 & HOCH ₂ CH ₂ O ₂ CC (CH ₅ ) = CH ₂ and CH ₂ = CHCONHCh ₂ OH and "has an inherent viscosity of 0.270, determined on a 0.5 percent solution in trichlorotrifluoroethane at 30 ° C.

Example 8

The procedure is as in Example 1 using 128 parts of R ^ CH ₂ CH ₂ O ₂ CCH = CH ₂ and 32 parts of trifluoroethyl acrylate. The polymer obtained in this way contains 80 $> RfCH ₂ CH ₂ O ₂ CCH = CH ₂ , 20 ? * CP ₅ CH ₂ O ₂ CCH = CH ₂ and 0.25 & HOCH ₂ CH ₂ O ₂ CC (CH ₅ ) = each CH ₂ and CH ₂ = CHONHCh ₂ OH and has an inherent viscosity of 0.56, determined on a 0.5 percent solution in trichlorotrifluoroethane at 30 ° C.

Example 9

Example 1 is followed using 152 parts of RfCH ₂ CH ₂ O ₂ CCH = CH ₂ and 8 parts of CP ₅ CP ₂ CH ₂ O ₂ CCH = CH ₂ . The polymer obtained in this way contains 95 Ί> RfCH ₂ CH ₂ O ₂ CCH = CH ₂ , 5 # CP ₅ CP ₂ CH ₂ O ₂ CCH = CH ₂ and 0.25 $> HOCH ₂ CH ₂ O ₂ CC (CH ₅ ) = CH ₂ and CH ₂ = CHCONHCH ₂ Oh and has an inherent viscosity of 0.27, determined on a 0.5 percent solution in trichlorotrifluoroethane at 30 ° C.

Example 10

The procedure is as in Example 1 using 160 parts of RfCH ₂ CH ₂ O ₂ CCH = CH ₂ , 0.095 parts of HOCH ₂ CH ₂ O ₂ CCH = CH ₂ and 0.145 parts of a 60 percent aqueous solution of CH ₂ = CHCONH-

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QR.r4-6.68

1S

CH ₂ OH with release of CPjCH ₂ O ₂ CCH = CH ₂ . The polymer obtained in this way does not fall within the scope of the invention, but is only produced for comparison purposes. It contains $ 99.5> R ₁ -CH ₂ CH ₂ O ₂ CCH = CH ₂ and each 0.25 # CH ₂ = C (CH ₅ ) CO ₂ CH ₂ CH ₂ Oh and CH ₂ = CHCONHCH ₂ Oh and has an inherent viscosity of 0.475, / determined on a 0.5 percent solution in trichlorotrifluorine

ethane at 30- C.

Example

Aqueous emulsions of the polymers according to Examples 1 and 2 are prepared by adding water. The emulsions contain 6.00 # Polymerisatfeststoffe (5.4 i "active ingredient in the form of polymerized R ^ CH ₂ CH ₂ O ₂ CCH = CH _2). The emulsions are used to prepare two batches (A and B) that are examined for the oil and water repellency that they impart to poplin fabric. .

Bee components of the approaches

1. Emulsion of the polymer according to Example 1

2 emulsion of the polymer according to example 2

3. TPermafresh "183

4. Catalyst

5. Stabilizer

Amount of components in batch A, $> OWF »

2 or 3 i » Polymerisatauf would take

12.0 2.3 0.05

Amount of components in batch B, i » OWP *

2 or 3 $> polymer uptake

12.0 2.3 0.05

* QWF « based on the weight of the fabric.

1. Polymer of Example 1:

90 # R _f CH ₂ CH ₂ O ₂ CCH = CH ₂ , 10 $ CP ₃ CH ₂ O ₂ CCH = CH ₂ and 0.25 # HOCH ₂ CH ₂ O ₂ CC (CH ₃ ) = CH ₂ and each. CH ₂ = CHCONHCH ₂ Oh

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2. Polymer of Example 2: 90 # R _f CH ₂ CH ₂ O ₂ CCH = CH ₂ , 10 # CP ₅ CP ₂ CH and each 0.25 $> HOCH ₂ CH ^; ₂ O ₂ CC (CH, ^ CH ₂ and. CH ₉ = CHCONHCH ₉ OHf

3. "" Permafresh "183:

Non-iron resin of the, composition

HIGH ₂ -N CHOH

^{C = C} \ ^ CHOH

HIGH ₂

4 catalyst:

27 percent aqueous zinc nitrate solution

5 Stabilizer:

30 percent aqueous solution of the hydrochloride of

° 18 ^H 37 ^N C x + y = 15

'(CH ₂ CH ₂ O) ₇ H'

Samples of dyed poplin fabric by the thermosol from 65 i "polyethylene terephthalate and 35 $> Cotton; are padded with batches A and B, the wet pick-up being controlled by adjusting the squeegee rollers (generally about 50 # wet pick-up) so that the concentration of the polymer in question on the fiber (# ÖWP) has the values given for the batches. The treated fabrics are air-dried and heated to 171 ° C for 10 minutes. Then the oil and water repellency is examined.

The water repellency of the treated fabric samples is determined according to the A.A.T.C.C. test standard 22-1952 of the American Association. of Textile Chemists and Colourists. A value of 100 means no penetration or adhesion of water to the surface, a value of 90 means little random sticking or wetting, etc.

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OR-4668

The examination of the oil repellency is as follows carried out. A drop is carefully placed on the fabric lying on a flat horizontal surface applied to the solution to be examined. After 3 minutes, an inspection is carried out to determine whether it is penetrating or sucking in der.Flüssigkeit has taken place in the textile fabric. To the To facilitate investigation, the test solutions contain something oil soluble blue dye. The type of test solutions is given below. Nujol is a purified petroleum distillate. All values of 5 and more mean good or excellent; all values of 1 or more mean that the substance is for can be used for certain purposes. For example, if a treated tissue rejects solutions 1 to 6, the solution No. 7, however, does not reject it, it is rated 6.

oil repellent
value Test solution 5 70 Surface tension,
dynes / cm at 25 ° C ^: 9 n-hexane
I. 5 70 19.2 8th I.
n-heptane 20.0 7 ... n-octane. 21.8 6th n-decane 23.5 VJl n-dodecane . ■ - \ 25.0 ■ 4 n-tetradecane 26.7 3 n-hexadecane 27.3 2 Mixture of same
Share hexadecane
and Nujol •
28.7 1 Nujol 31.2 The results are the following: Polymer emulsion, approach A
% OWF. Oil water Approach B
oil ^: water. 2.0 . 5 70 3.0 6 70

- 17 -

009837/2123

OR-4668

B e i s ρ i e 1 12

After the test according to Example 11, samples of the same treated fabrics are subjected to home washing and dry cleaning, as described below.

Home laundry (HW): A Kenmore washing machine, model 600, is loaded with 1.8 kg of laundry and 29 g of detergent and wetting agent ("TIDE"). The machine is set to a hot wash cycle (12 minute period) and a Warrao rinse cycle (12 minutes). The total washing and rinsing time is 40 minutes. In the HQimwnaohe with air drying (HWLT), the spun off substances are dried at room temperature. For home washing with drum drying (HWTT), the spun off substances are circulated in a household drying drum at 69 to 71 ° G.

Dry cleaning (TR): The sample is kept in motion for 120 minutes in Tetraohloräthylen, which contains a commercial dry cleaning detergent in an amount of 1.5 g per 100 ml, extracted with tetrachlorethylene, dried for 3 minutes at 66 ° C in the drum and ironed at 149 ° C for 15 seconds on each side.

The samples are then examined according to Example 11. The results can be found in Table I.

- 18 -

009837/2123

OR-4668 T 13th 1 e 201.1 311 What
ser Polymer-
enrulsion,
3 Ϊ * OWP What
ser Approach B What
ser
* · · Polymer-
emulsion,
3 # OWP What
ser a b e 1 ■ 70 oil 70 Polymer-
emulsion,
2 i> OWP 70 oil 70 oil and j I Water repellency TO 2 - oil 70 4th - Approach A 7 ° - 70 2 70 - 70 Number and type of
Cleaning and
Trooken operations Polymer-
emulsion,
2 i » OWP 70 4th - 2 70 5 - oil 70 - - 3 70 - - 1 HWLT 2 70 - - 2 70 - - 5 HW-T LT * 2 70 - 70 2 70 - 70 1 HWTT. 3 70 5 - 2 70 . 6th - 5 HW-5 TT 1 70 - - - 4th 70 - - 10 HW-10 TT 2 4th - 20 HW-20 TT 2 1 1 TR 3 10 TR 4th 20 TR 1

♦ 1 LT after the last home wash. - Attempt "not carried out.

example

Samples of the batches A and B, as in Example 11, treated - Deleted tissues are removed from the process before the heat treatment and instead for the periods indicated placed in an oven at 135 ° C and then examined for their oil repellency. Tissue that is less than 40 seconds stay in the oven, you are still nose; but in all cases the fabrics removed from the oven are allowed to air dry at constant humidity before their oil repellency is determined. The results can be found in Table II.

-19 -

00 9837/2123

OR-4668

Tabel

II

oil repellency Approach B.
Polymer emulsion,
2 i » OWP Approach A
Polymer emulsion,
2 i » OWF 1 1 2 CVl 3 CVI 3 '· " 4th 3 4th . 3 4th

Seconds in the oven

10

20th

40

80 160 300

It should be noted that this involves non-iron treatments before the non-iron resin is fixed by heat treatment acts. Such heat treatments are usually carried out at 150 to 177 ° C for 10 minutes; by heating in the oven 135 ° 0 the non-iron resin is not "fixed". One therefore sees from the results of Table II that the fabrics, even if they are not yet completely dry, have a certain oil repellency, which increases further on drying so that the fabrics are already protected without fixing the non-iron resin.

Example 14

Samples of fabrics treated with batches A and B according to Example 11 and heat-treated are subjected to dry cleaning, but the process stages of drying and ironing are omitted. After removing the Excess solvent will flatten the fabrics for the specified number of seconds on each side introduced and then examined for their oil repellency. The results can be found in Table III.

- 20 -009837/2123

t
OR-4668 Ii
Tabel 2011 311
III Anaatz B
Pblymeremuleion,
2 # OWP oil repellency 4th
4th
4.,. "
4th Seconds
in the press Approach A
Polymer emulsion,
2 fo OWP .0
5
ok
15th 4 ■
4th
4th
. 4th

So the fabric already shows oil repellency without to be heated again.

While the repellency of non-iron fabrics normally with dry cleaning disappears and duroh re-r must be produced by heating, the copolymers behave different according to the invention. From the results of Table III it can be seen that the treated fabrics, Maintain their oil repellency during dry cleaning without having to be heated afterwards.

Example 15

Samples of tissues treated with batches A and B are made heat-treated and once dry-cleaned (Examples 11 and 12). Then the samples are placed in the Wyco tear tester subject to abrasion * and oil repellency on it examined. The results can be found in Table IV.

- 21 -

009837/2123

OR-4668 U Z. U I e IV Approach B
Polymer emulsion,
2 $ OWP T a b e 1 1 Oil repellency 6th Approach A
Polymer emulsion,
2 i> OWP 6th number of
Abrasion cycles 7th 6,; O ' 6th 5 500 - - 1000 6th 4th 1500 3 3000 3 5000

This results in good abrasion resistance.

Example 16

Emulsions of the polymers according to Examples 3 to 10 are prepared according to Example 11 and diluted to an active ingredient content of RfCH ₂ CH ₂ O ₂ CCH = CH ₂ in polymerized form of 5 »4 #. The emulsions are then used to prepare eight batches, the ingredients of which are as follows:

Component · #. OWP

"Permafresh" 183 * 12.0 Catalyst* 2.4 Stabilizer* 0., 05 an emulsion of one of the Polymer sate according to example 3 bis 10 2 or

* as in example 11.

The tissue samples are padded and examined according to Example 11; the results can be found in Table V.

- 22 009837/2123

Tabel

ro
οι

Emulsion of

Polymer according to example 3 (95 t RfCHgCH ₂ O ₂ CCH = CHg, 5 t H (CPg) ₂ CH ₂ O ₂ CCH = CHg, each 0.25 1> HOCH ₂ CH ₂ O ₂ CC (CH ₅ ) = CH ₂ and CH ₂ = CHCONHCH ₂ Oh)

Polymer according to example 4 (90 + RfCH ₂ CH ₂ O ₂ CCH = CH ₂ , 10 i> H (CPg) ₂ CH ₂ O ₂ CCH = CH ₂ , each 0.25 £ CH ₂ = C (CH ₅ ) CO ₂ CH ₂ -OH ₂ OH and CH ₂ = CHCONHCH ₂ Oh)

Polymer according to Example 5 (80? TRfCH ₂ CH ₂ 0 ₂ CCH = CH ₂ , \ 20 f H (CPg) ₂ CH ₂ O ₂ CCH = CH ₂ , each 0.25 <f> CH ₂ = C (CH ₅ ) CO ₂ CH ₂ - ¹ CH ₂ OH and CH ₂ = CHCONHCHgOH)

initially
oil water 70
70 Repellency HWLT
water oil HWTT
water oil 1 TR
water 00 OWP 5
5 Si 50
70 3
4th 50
70 5 50
70 2
3 2
2

2 5 70 2 50 3 50 4th 50 3 6th 70 2 70 4- 70 6th 50

5 70 3 50 3 70 5 50 6th 70 4th 70 5 70 5 50

O ι co »Ο fa" -α.

Emulsion of

Polymer according to example 6 (95 ί RfCH ₂ CH ₂ O ₂ CCH = CH ₂ , 5 * (CP ₅ J ₂ CHO ₂ CCH = CH ₂ , each 0.25 $ CH ₂ = C (CH ₅ ) CO ₂ CH ₂ - CH ₂ OH and CH ₂ = CHCONHCh ₂ OH)

Polymer according to example 7 (95 % RfCH ₂ CH ₂ O ₂ CCH = CH ₂ , 5 tf CP ₅ CH ₂ O ₂ CCH = CH ₂ , each 0.25 $> HOCH ₂ CH ₂ O ₂ CC (CH ₅ ) = OH ₂ and CH ₂ = CHCONHCH ₂ Oh)

Polymer according to example ^ (80 * RfCH ₂ CH ₂ O ₂ CCH = CH ₂ , ^l

20 Ji CP ₅ CH ₂ O ₂ CCH = CH ₂ ,

0.25 yrs each

^[ 2

T ate lie V 70
70 (Port setting) HWTT
water oil 1 TR
water -46 70
70 3
4th 50
70 σ »
CD OWP initially
oil water Refusal 2
3 VJl 4 »·. ' 1 HWlT 1
'oil water oil 2 50 2
2 50 3

uad CH ₂ = CHCONHCH ₂ Oh)

HIGH ₂ CH ₂ O ₂ CC (CH ₅ ) = CH _{2 2} 4
6th

50
80

70

2
2

50 70

50

50 70

3 5

70

label 1 e

τ? ι ". ro ul

Emulsion of

Polymer according to example {95 f R ₁₁ GH ₂ CJH ₂ Q ₂ CGH = CH ₂ , 5 f CP ₃ CF ₂ CH ₂ O ₂ CCH = CH ₂ , each 0.25 | £ HOCH ₂ CH ₂ O ₂ CC (CH ₅ ) = CH ^ i ^ d. ^ H ₂ = GHGOIiHCH ₂ OH) PoJLyiDejiisai; according to the example (99.5196% GH ₂ CH ₂ 0 ₂ GCH = CH ₂ , each. 0.25-, ^ CH ₂ = C (CH ₃ ) Ca ₂ CH ₂ -CHOH & CH ₂ = GHGOIiHCH ₂ OH)

OWF

2 3

V (continued )

Repellency

HWLT 1 HWTT

oil water oil water

4th 5

70 70

70

ao

50 50

50 50

2 3

2 3

50 70

70 70

oil

50 50

50 50

ro. CD

? ni 1311

OR-4668 - TO MJ M

Example 17

Pad baths are produced using the approaches given below. Textiles are padded with these baths, the wet pick-up by setting the nip rollers to the weight percentages given in the table below Admission values for the individual components is regulated. The treated tissues are specified for Maintained periods of time in an oven at 135 C, followed by repellency is determined. Tissues that have been in the oven for 40 seconds or less are still wet. In all cases will be the fabric is dried in the air at constant humidity to constant weight before the repellency is determined. The results can be found in Table VI.

Approaches, $> OWF

12th , 0 12, 0 12th , 0 12th , 0 2 , 3 2, 3 CVJ , 3 2 , 3 0 , 04 O, 04 0 , 04 0 , 04

Components A BC D

Dispersion with 6.21% polymer according to Example 1 2.5 3.5

Dispersion with 6.21 # polymer according to Example 10 2.5 3.5

"Permafresh" 183 according to example 11

Catalyst according to Example 11
Stabilizer according to Example 11

The tissues treated are the following:

Fabric A = the "poplin fabric made of 65 # polyester and 35 $ cotton" described in Example 11.

Fabric B = undyed, mercerized cotton, neutral pH value, no whitening agents, 3.22 m / kg, 116.8 cm wide.

The results can be found in the table below. In this case, the oil repellency is determined by two different methods: "30 sec." refers to the test

- 26 009837/2123

OR-4668 ^Γ

norm 118-1966Τ, while "3 min." relates to the modification of this standard test described in Example 11 using blue-colored oils. The water repellency is determined according to the test standard 22-1952 described in Example 11 . ■ »

Tabel VI "3 min." Time in the oven, Sec. approach oil repellent vents 3 Fabric A "30 sec." 3 10 A. 4th 20th A. 3 4th 40 A. 4th 4 ' 60 A. 4th 4,. 10 B. - 5 20th ■ 'B 5 2 40 B. 5 2 10 C. , 5 3 20th C. 2 4th 40 C. 2 3. 60 C. 4 - 2. 10 D. _- ,. 5 ' 20th D. 3 40 D. _ 3 6th

- 27 009t37 / 1123

Table VI (continued)

^ in the oven,
Sec. Approach water repellency 50; (each B 50 10 B. 50; 20th B. 50 40 B. 70 '' 60 B, O 80 B. O 10. D. 50 ^! ! 20th D. 50 40 D i 70 ; 60 D. ^! 80

- 28 009 837/2123

Claims (7)

Claims 1 · Oil and water repellent polymer, thereby marked ι that it is essentially ' (a) to about 75 to 98 percent by weight of units derived from monomers of the general formula R _f CH ₂ CH ₂ O ₂ -CGH = CH ₂ , in which R _{f is} a perfluoro "alkyl group with 4 to 14 carbon atoms, (b) to about 25 to 2 percent by weight of units derived from monomers of the general formula R0 ₂ CCH = iCH ₂ , in which R means F (CFg) _n CH ₂ - (n = 1 or 2), HCF ₂ CF ₂ CH ₂ - or (CF ₅ J ₂ CH, and (0) to-about 0 to 5 percent by weight from units I ι - "which is derived from monomers .. of the" general formula CH ₂ = CR ¹ CONH-R ² OH, CH ₂ = CR ¹ CO ₂ R ³ OH, CH ₂ = CR ¹ CO ₂ R ⁴ or mixtures thereof, whereby R is a hydrogen atom or a methyl group, 2 ' R is an alkylene radical with 1 to 4 carbon atoms, an alkylene radical having 2 to 4 carbon atoms and an E
means. R is an epoxyalkyl group having 3 to 4 carbon atoms - 29 -009837/2123 OR-4668 2. Polymer according to claim 1, characterized in that R- in the polymer units according to part (a) has the general formula F (CF ₀ J ₀ , where a has a value of from 4 to 14). 3 «Polymer according to claim 2, characterized in that s in the formula F (CF ₂ ) has the values 6, 8, 10, 12 and 14 in a weight ratio of 35/30/18/8/3. 4. Process for the preparation of the polymers according to claim 1, characterized in that one (a) about 75 to 98 parts by weight of monomers of the general formula R ^ CH ₂ CH ₂ O ₂ CCH = CH ₂ , in which R _{f is} a perfluoroalkyl group with 4 to 14 carbon atoms, (b) about 25 to 2 parts by weight of monomers of the general formula RO ₂ CCH = CH ₂ , in which R is F (CFg) _n -CH ₂ - (n = 1 or 2), HCF ₂ CF ₂ CH ₂ - or ( CF ^) has ₂ CH, and (o) e ^ wa 0 to 5 weight points monomers of the general Formula CH ₀ = CR ¹ CONH-R ² OH, CH ₉ = CR ¹ CO ₉ R ³ OH, 14th
CH ₂ = CR CO ₂ R or mixtures thereof polymerized, where R is a hydrogen atom or a methyl group, ο
R is an alkylene radical with 1 to 4 carbon atoms, ■ z _ R ^ is an alkylene radical with 2 to 4 carbon atoms and R is an epoxyalkyl group with 3 or 4 carbon v. atoms means. 5. The method according to claim 4, characterized in that according to part (a) monomers are used in which R _f , corresponds to the general formula F (CF ₀ ) _, where s is a £ p Has value from 4 to 14. 6. "Method according to claim 5" characterized in that monomers are used in which s in the radical F (CF ₀ ) "the values 6, 8, 10, 12 and 14 in the weight ratio - 30 -009837/2 123 OR-4668 35/30/18/8/3. 7. Textile fabric, characterized in that it has a Polymer according to claim 1 has been treated. - 31 -0 0 9837/2123